Nothing Special   »   [go: up one dir, main page]

EP1777051B1 - Polyurethane foams for insulating pipes - Google Patents

Polyurethane foams for insulating pipes Download PDF

Info

Publication number
EP1777051B1
EP1777051B1 EP06121729A EP06121729A EP1777051B1 EP 1777051 B1 EP1777051 B1 EP 1777051B1 EP 06121729 A EP06121729 A EP 06121729A EP 06121729 A EP06121729 A EP 06121729A EP 1777051 B1 EP1777051 B1 EP 1777051B1
Authority
EP
European Patent Office
Prior art keywords
pipe
polyol mixture
medium
polyol
process according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP06121729A
Other languages
German (de)
French (fr)
Other versions
EP1777051A1 (en
Inventor
Christof Grieser-Schmitz
Carsten Ellersiek
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to PL06121729T priority Critical patent/PL1777051T3/en
Publication of EP1777051A1 publication Critical patent/EP1777051A1/en
Application granted granted Critical
Publication of EP1777051B1 publication Critical patent/EP1777051B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/36—Feeding the material to be shaped
    • B29C44/38—Feeding the material to be shaped into a closed space, i.e. to make articles of definite length
    • B29C44/385—Feeding the material to be shaped into a closed space, i.e. to make articles of definite length using manifolds or channels directing the flow in the mould
    • B29C44/386—Feeding the material to be shaped into a closed space, i.e. to make articles of definite length using manifolds or channels directing the flow in the mould using a movable, elongate nozzle, e.g. to reach deep into the mould
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
    • B29C44/12—Incorporating or moulding on preformed parts, e.g. inserts or reinforcements
    • B29C44/1228—Joining preformed parts by the expanding material
    • B29C44/1242—Joining preformed parts by the expanding material the preformed parts being concentric
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/482—Mixtures of polyethers containing at least one polyether containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4829—Polyethers containing at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
    • C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
    • C08G18/5027—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups directly linked to carbocyclic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2101/00—Manufacture of cellular products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/0058—≥50 and <150kg/m3

Definitions

  • Pipe insulated with polyurethane foams are known in the art and, for example, in EP-A-865 893 and DE-A-197 42 012 described.
  • the majority of pre-insulated pipes that use PUR foam for insulation is produced by means of discontinuous pipe-in-pipe production.
  • the medium pipe usually steel
  • the outer sheath usually polyethylene
  • this annular gap is filled with polyurethane foam.
  • the slightly inclined double tube is provided with end caps, which are equipped with vent holes.
  • the liquid reaction mixture is filled in the annular gap by means of a polyurethane metering which flows down in still liquid form in the pipe gap until the reaction begins. From this time, the further distribution takes place by flowing the slowly rising in viscosity foam until the material is reacted.
  • the object of the invention was therefore to provide a polyurethane system which can be advantageously used in the production of insulated pipes and there leads to a polyurethane foam with very good compressive strength (> 0.3 N / mm 2 according to EN 253), with an excellent Centering of the steel pipe (medium pipe) is made possible.
  • the polyol mixture used in the reaction may usually contain (b1) polyols, (b2) catalysts and optionally (b3) chemical blowing agents, (b4) crosslinking agents, (b5) chain extenders and / or (b6) additives.
  • the polyol mixture consisting of (b1) polyols, (b2) catalysts and optionally (b3) chemical blowing agents, (b4) crosslinking agents, (b5) chain extenders and / or (b6) additives preferably has a viscosity of less than 3000 mPas, preferably less than 2400 mPas, more preferably less than 2200 mPas, measured according to DIN 53019 at 20 ° C, on.
  • This viscosity specification refers to polyol mixtures (b) which, as shown, contain no physical blowing agents. Values of 200 mPas, preferably 400 mPas, particularly preferably 600 mPas, measured according to DIN 53019 at 20 ° C., have proven to be useful as the lower limit of the viscosity.
  • the viscosity information of the polyol mixture (b) given above refers to the viscosity of the polyol mixture (b) without the addition of physical blowing agents.
  • the isocyanate component (a) used are the customary aliphatic, cycloaliphatic and in particular aromatic di- and / or polyisocyanates. Preferably used are tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI) and in particular mixtures of diphenylmethane diisocyanate and polyphenylene polymethylene polyisocyanates (crude MDI).
  • the isocyanates may also be modified, for example by incorporation of uretdione, carbamate, isocyanurate, carbodiimide, allophanate and in particular urethane groups.
  • the isocyanate component (a) can also be used in the form of polyisocyanate prepolymers.
  • prepolymers are known in the art.
  • the preparation is carried out in a manner known per se by reacting polyisocyanates (a) described above, for example at temperatures of about 80 ° C., with compounds containing isocyanate-reactive hydrogen atoms, preferably polyols, to form polyisocyanate prepolymers.
  • the polyol-polyisocyanate ratio is generally chosen so that the NCO content of the prepolymer 8 to 25 wt .-%, preferably 10 to 22 wt .-%, particularly preferably 13 to 20 wt .-% is.
  • the isocyanate component (a) is chosen to have a viscosity of less than 600 mPas, preferably from 100 to 450, especially preferably from 120 to 350, in particular from 180 to 320 mPas, measured according to DIN 53019 at 20 ° C having.
  • polyols in addition to the polyols according to the invention, polyols known in general for this purpose can be used.
  • polyols known in general for this purpose can be used.
  • compounds having at least two isocyanate-reactive groups, ie having at least two hydrogen atoms reactive with isocyanate groups are suitable.
  • examples include compounds with OH groups, SH groups, NH groups and / or NH 2 groups.
  • Preferred polyols are compounds based on polyesterols or polyetherols.
  • the functionality of the polyetherols and / or polyesterols is generally 1.9 to 8, preferably 2.4 to 7, particularly preferably 2.9 to 6.
  • the polyols (b1) preferably have a hydroxyl number of greater than 70 mg KOH / g, preferably greater than 100 mg KOH / g, more preferably greater than 120 mg KOH / g.
  • the upper limit of the hydroxyl number has generally proven to be 1000 mg KOH / g, preferably 900 mg KOH / g, especially 800 mg KOH / g.
  • Component (b1) preferably comprises polyetherpolyols prepared by known processes, for example by anionic polymerization with alkali metal hydroxides, such as sodium or potassium hydroxide or alkali metal alkoxides, such as sodium methylate, sodium or potassium ethylate or potassium isopropylate as catalysts and with the addition of at least one starter molecule 2 to 8, preferably contains 3 to 8 bonded reactive hydrogen atoms, or by cationic polymerization with Lewis acids, such as antimony pentachloride, boron fluoride etherate, inter alia or bleaching earth are prepared as catalysts from one or more alkylene oxides having 2 to 4 carbon atoms in the alkylene radical.
  • alkali metal hydroxides such as sodium or potassium hydroxide or alkali metal alkoxides, such as sodium methylate, sodium or potassium ethylate or potassium isopropylate
  • Lewis acids such as antimony pentachloride, boron fluoride etherate, inter alia
  • Suitable alkylene oxides are, for example, tetrahydrofuran, 1,3-propylene oxide, 1,2- or 2,3-butylene oxide, styrene oxide and preferably ethylene oxide and 1,2-propylene oxide.
  • the alkylene oxides can be used individually, alternately in succession or as mixtures.
  • starter molecules are alcohols, such as glycerol, trimethylolpropane (TMP), pentaerythritol, sucrose, sorbitol, and amines such as methylamine, ethylamine, isopropylamine, butylamine, benzylamine, aniline, toluidine, toluene diamine (TDA), naphthylamine, ethylenediamine, Diethylenetriamine, 4,4'-methylenedianiline, 1,3-propanediamine, 1,6-hexanediamine, ethanolamine, diethanolamine, triethanolamine and the like.
  • TMP trimethylolpropane
  • pentaerythritol sucrose
  • sorbitol amines
  • amines such as methylamine, ethylamine, isopropylamine, butylamine, benzylamine, aniline, toluidine, toluene diamine (TDA), naphthylamine,
  • condensation products of formaldehyde, phenol and diethanolamine or ethanolamine, formaldehyde, alkylphenols and diethanolamine or ethanolamine, formaldehyde, bisphenol A and diethanolamine or ethanolamine, formaldehyde, aniline and diethanolamine or ethanolamine, formaldehyde, cresol and diethanolamine or Ethanolamine, formaldehyde, toluidine and diethanolamine or ethanolamine and formaldehyde, toluene diamine (TDA) and diethanolamine or ethanolamine and the like can be used.
  • Diethylene glycol, glycerol and pentaerythritol are preferably used as the starter molecule.
  • the polyol mixture may optionally contain catalysts as component (b2).
  • the catalysts (b2) used are usually compounds which accelerate the PUR and / or PIR reaction.
  • organic tin compounds such as tin (II) salts of organic carboxylic acids, and / or basic amine compounds, preferably tertiary amines, such as triethylamine, and / or 1,4-diaza-bicyclo- (2,2,2 ) octane.
  • the catalysts are generally used in an amount of 0.001 to 5 wt .-%, in particular from 0.05 to 3.5 wt .-% catalyst, based on the weight of component (b).
  • Particularly preferred before the reaction of the isocyanate component (a) with the polyol mixture (b) is between 0.01 and 3.5 wt .-% N, N ', N "-Tris (dimethylaminopropyl) hexahydrotriazine (CAS number 15875-13 5) in the polyol mixture (b), wherein the weights are based on the total weight of the polyol mixture (b) containing N, N ', N "-Tris (dimethylamino-propyl) hexahydrotriazine.
  • N - ((2-hydroxy-5-nonylphenyl) methyl) -N-methyl-monosodium salt (CAS number 56968-08-2) as catalyst (b2) also dimethylcyclohexylamine (CAS number 98-94-2).
  • N - ((2-hydroxy-5-nonylphenyl) methyl) -N-methyl-monosodium salt (CAS number 56968-08-2) as catalyst (b2) also methylbis (2-dimethylaminoethyl) amine (CAS number 3030-47-5) and / or N, N, N ', N'-tetramethyl-2,2'oxybis (ethylamine) (CAS number 3033-62-3).
  • the polyol mixture may further optionally contain as component (b3) chemical blowing agents.
  • chemical blowing agents water or carboxylic acids, especially formic acid, are preferred as the chemical blowing agent.
  • the chemical blowing agent is generally used in an amount of 0.1 to 5 wt .-%, in particular from 0.5 to 3.0 wt .-%, based on the weight of component (b).
  • the polyol mixture may contain physical blowing agent.
  • This refers to compounds which are dissolved or emulsified in the starting materials of polyurethane production and evaporate under the conditions of polyurethane formation. These are, for example, hydrocarbons, halogenated hydrocarbons, and other compounds, such as perfluorinated alkanes, such as perfluorohexane, chlorofluorocarbons, and ethers, esters, ketones and / or acetals. These are usually used in an amount of 1 to 30 wt .-%, preferably 2 to 25 wt .-%, particularly preferably 3 to 20 wt .-%, based on the total weight of components b).
  • the polyol mixture (b) contains crosslinker as component (b4).
  • Crosslinkers are understood as meaning compounds which have a molecular weight of 60 to less than 400 g / mol and have at least 3 isocyanate-reactive hydrogen atoms. An example of this is glycerin.
  • the crosslinkers are generally used in an amount of from 1 to 10% by weight, preferably from 2 to 6% by weight, based on the total weight of the polyol mixture (b) (but without physical blowing agents).
  • the polyol mixture (b) contains, as constituent (b5), chain extenders which serve to increase the crosslinking density.
  • Chain extenders are understood as meaning compounds which have a molecular weight of 60 to less than 400 g / mol and have 2 isocyanate-reactive hydrogen atoms. Examples of these are butanediol, diethylene glycol, dipropylene glycol and ethylene glycol.
  • the chain extenders are generally used in an amount of from 2 to 20% by weight, preferably from 4 to 15% by weight, based on the total weight of the polyol mixture (b) (but without physical blowing agents).
  • the components (b4) and (b5) can be used in the polyol mixture individually or in combination.
  • the polyurethane foams according to the invention are obtainable by reacting the polyurethane system according to the invention.
  • the polyisocyanates (a) and the polyol mixture (b) are generally reacted in amounts such that the isocyanate index of the foam is 90 to 250, preferably 100 to 200.
  • the components (a) and (b) of the polyurethane system are chosen so that the resulting foam a compressive strength (density 60 kg / m 3 ) of greater than 0.25 N / mm 2 , preferably greater than 0.28 N / mm 2 , more preferably greater than 0.30 N / mm 2 , measured according to DIN 53421.
  • additives (b6) can also be incorporated into the polyurethane system according to the invention.
  • Additives (b6) are understood to be the auxiliaries and additives known and customary in the prior art, but without physical blowing agents. Mention may be made, for example, of surface-active substances, foam stabilizers, cell regulators, fillers, dyes, pigments, flame retardants, antistatic agents, hydrolysis protectants and / or fungistatic and bacteriostatic agents Substances. It should be noted that the preferred viscosity ranges of component (b) given above relate to a polyol mixture (b) including any added additives (b6) (but excluding any added physical blowing agent).
  • the polyurethane systems according to the invention are preferably used for producing insulated pipes, for example district heating pipes.
  • the invention thus relates to the use of the polyurethane system according to the invention for the production of insulated pipes.
  • the polyurethane system according to the invention for the production of insulated composite jacketed pipes for buried district heating networks according to DIN EN 253 is used.
  • the medium pipe (i) is generally a steel pipe having an outer diameter of 1 to 120 cm, preferably 4 to 110 cm and a length of 1 to 24 meters, preferably 6 to 16 meters.
  • a layer of insulating material (ii) containing the polyurethane foam according to the invention Arranged on the outside of the medium pipe is a layer of insulating material (ii) containing the polyurethane foam according to the invention.
  • This layer generally has a thickness of 1 to 20 cm, preferably 2 to 10 cm.
  • the layer of insulating material has a total apparent density of 55 to 100 kg / m 3 , preferably from 60 to 75 kg / m 3 , particularly preferably from 60 to 67 kg / m 3 .
  • Total gross density refers here to the raw density distribution over the pipe cross-section and the pipe length.
  • Compression is the quotient of the total filling density of the pipe gap divided by the free-blown core raw density determined on an uncompressed foam body.
  • This densification can be achieved by adjusting the reaction profile of the foam so that the fresh foam compresses the already filled foam. In other words, the foam compresses from the inside out.
  • This compaction offers the advantage that higher compressive strengths and improved centering of the carrier pipe can be achieved.
  • the layer of insulating material (ii) containing the polyurethane foam of the invention has a thermal conductivity of less than 27 mW / mK, preferably from 20 to 26.0, particularly preferably 20 to 24 measured according to EN ISO 8497.
  • the jacket tube (iii) surrounds the layer of insulating material and is generally made of plastic, such as polyethylene, and usually has a thickness of 1 to 30 mm.
  • the inner diameter of the jacket tube is generally 6 to 140 cm, preferably 10 to 120 cm.
  • the jacket tube (iii) may optionally consist of several layers, which are merged during the extrusion process.
  • An example of this is the introduction of multilayer films between PUR foam and PE sheath, wherein the film contains at least one metallic layer to improve the barrier effect.
  • Suitable jacket tubes of this type are in EP-A-960 723 described.
  • the insulated pipe is an insulated composite casing pipe for buried district heating networks, which meets the requirements of DIN EN 253.
  • the isocyanate component (a) and the polyol mixture (b) by means of a mixing head, which is moved axially between the casing pipe and medium pipe, enter.
  • the mixing head preferably serves as a spacer between carrier pipe and casing pipe.
  • a guide ring is pushed with the mixing head between the medium pipe (usually steel) and the outer jacket tube (usually polyethylene), which is axially movable and also serves as a spacer between the carrier pipe and casing pipe.
  • the annular gap between medium pipe and casing pipe is filled with polyurethane foam due to its good insulating properties.
  • the filling in the annular gap is preferably carried out by means of a polyurethane metering machine, which enters the liquid reaction mixture via the mixing head in still liquid form.
  • Compressive strengths can be achieved which are above 0.25 N / mm 2 .
  • tubes are produced which have compressive strengths> 0.3 N / mm 2 and correspond to EN 253.
  • insulated pipes can be achieved with a centering of the carrier pipe, which meet the requirements of Table 7 - Coaxiality tolerance depending on the nominal outside diameter, EN 253: 2003
  • the inventive polyol A (Examples 1 and 3) has a clearly positive effect.
  • the limit of EN 253 of 0.3 N / mm 2 could be skipped.
  • the centering of the medium pipe can also be significantly improved by the polyol and is in the tested pipe dimension of 60.3 / 125mm below the limit of 3mm.
  • the addition of the preferred catalyst (Curithane 52, Examples 1 and 2) leads to a significant improvement in the compressive strength compared to the standard formulation and a centering, which is improved, but the EN 253 barely reached. Both characteristics together lead to improved properties of the insulated pipe and thus to clear advantages and safe exceeding of the limit values of EN 235: 2003.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Thermal Insulation (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

Insulated pipe, comprises a medium pipe; polyurethane-foam material, obtained by reaction of an isocyanate component with a polyol mixture; and jacket pipe, where the polyol mixture comprises at least a polyether polyalcohol, which is obtained by the alkoxylation of saccharose, diethyleneglycol and optionally pentaerythrite and/or glycerin with ethylene oxide and/or propylene oxide, and exhibits a isocyanate functionality of greater than 3, a hydroxyl number of greater than 300 mg of potassium hydroxide (KOH)/g and a viscosity of less than 2500 mPas at 25[deg]C in accordance with DIN 53019. An independent claim is included for the preparation of insulated pipe comprising providing the medium pipe and the jacket pipe, where the medium pipe is arranged within the jacket pipe, and preparing the polyurethane-foam material.

Description

Die Erfindung betrifft gedämmte Rohre, aufgebaut aus

  1. i) Mediumrohr
  2. ii) Polyurethanschaumstoff erhältlich durch Umsetzung einer Isocyanatkomponente (a) mit einer Polyolmischung (b) und
  3. iii) Mantelrohr,
wobei die Polyolmischung (b) mindestens ein Polyetherpolyalkohol (b1i) enthält, dass erhältlich ist durch Alkoxylierung von Saccharose und Diethylenglykol und/oder Glycerin sowie gegebenenfalls Pentaerythrit mit Ethylenoxid und/oder Propylenoxid und das eine Funktionalität gegenüber Isocyanaten von größer 3, bevorzugt zwischen 3 und 4,5, eine Hydroxylzahl größer 300 mg KOH/g, bevorzugt zwischen 300 und 450 mg KOH/g, und eine Viskosität von kleiner 2500 mPas, bevorzugt zwischen 1500 und 2500 mPas, jeweils gemessen nach DIN 53019 bei 25°C, aufweist. Außerdem bezieht sich die Erfindung auf Verfahren zur Herstellung von gedämmten Rohren, umfassend die Schritte:
  1. 1) Bereitstellen von Mediumrohr und des Mantelrohrs, wobei das Mediumrohr innerhalb des Mantelrohrs angeordnet ist,
  2. 2) Herstellung eines Polyurethanschaumstoffes durch Umsetzung einer Isocyanatkomponente (a) mit einer Polyolmischung (b) zwischen Mediumrohr und Mantelrohr,
wobei die Polyolmischung (b) mindestens ein Polyetherpolyalkohol (b1i) enthält, dass erhältlich ist durch Alkoxylierung von Saccharose und Diethylenglykol sowie gegebenenfalls Pentaerythrit und/oder Glycerin mit Ethylenoxid und/oder Propylenoxid und das eine Funktionalität gegenüber Isocyanaten von größer 3, bevorzugt zwischen 3 und 4,5, eine Hydroxylzahl größer 300 mg KOH/g, bevorzugt zwischen 300 und 450 mg KOH/g, und eine Viskosität von kleiner 2500 mPas, bevorzugt zwischen 1500 und 2500 mPas, jeweils gemessen nach DIN 53019 bei 25°C, aufweist.The invention relates to insulated pipes, constructed from
  1. i) Medium pipe
  2. ii) polyurethane foam obtainable by reacting an isocyanate component (a) with a polyol mixture (b) and
  3. iii) jacket pipe,
wherein the polyol mixture (b) at least one polyether polyalcohol (b1i) that is obtainable by alkoxylation of sucrose and diethylene glycol and / or glycerol and optionally pentaerythritol with ethylene oxide and / or propylene oxide and having a functionality to isocyanates greater than 3, preferably between 3 and 4.5, a hydroxyl number greater than 300 mg KOH / g, preferably between 300 and 450 mg KOH / g, and a viscosity of less than 2500 mPas, preferably between 1500 and 2500 mPas, each measured according to DIN 53019 at 25 ° C. In addition, the invention relates to methods for producing insulated pipes, comprising the steps:
  1. 1) providing the medium pipe and the jacket pipe, wherein the medium pipe is arranged inside the jacket pipe,
  2. 2) production of a polyurethane foam by reacting an isocyanate component (a) with a polyol mixture (b) between medium pipe and jacket pipe,
wherein the polyol mixture (b) at least one polyether polyalcohol (b1i) that is obtainable by alkoxylation of sucrose and diethylene glycol and optionally pentaerythritol and / or glycerol with ethylene oxide and / or propylene oxide and having a functionality to isocyanates of greater than 3, preferably between 3 and 4.5, a hydroxyl number greater than 300 mg KOH / g, preferably between 300 and 450 mg KOH / g, and a viscosity of less than 2500 mPas, preferably between 1500 and 2500 mPas, each measured according to DIN 53019 at 25 ° C.

Mit Polyurethanschaumstoffen gedämmte Rohre sind im Stand der Technik bekannt und beispielsweise in EP-A-865 893 und DE-A-197 42 012 beschrieben.Pipe insulated with polyurethane foams are known in the art and, for example, in EP-A-865 893 and DE-A-197 42 012 described.

Der überwiegende Anteil an vorgedämmten Rohren, die PUR-Schaum zur Dämmung nutzen wird mit Hilfe der diskontinuierlichen Rohr-in-Rohr Produktion hergestellt. Im Rahmen dieses Verfahrens wird das Mediumrohr (in der Regel Stahl) mit sternförmigen Abstandshaltern versehen, die der Zentrierung des inneren Rohres dienen. Das Mediumrohr wird in das äußere Hüllrohr geschoben (in der Regel Polyethylen), so dass sich ein Ringspalt zwischen beiden Rohren ergibt. Aufgrund seiner hervorragenden Dämmeigenschaften wird dieser Ringspalt mit Polyurethanschaum gefüllt. Hierfür wird das leicht geneigte Doppelrohr mit Abschlusskappen versehen, die mit Entlüftungslöchern ausgestattet sind. Anschließend wird in den Ringspalt mittels einer Polyurethandosiermaschine das flüssige Reaktionsgemisch eingefüllt welches in noch flüssiger Form im Rohrspalt hinunter fließt bis die Reaktion einsetzt. Ab diesem Zeitpunkt findet die weitere Verteilung durch Fließen des langsam in der Viskosität ansteigenden Schaums statt, bis das Material ausreagiert ist.The majority of pre-insulated pipes that use PUR foam for insulation is produced by means of discontinuous pipe-in-pipe production. As part of this process, the medium pipe (usually steel) with star-shaped Provided spacers, which serve to center the inner tube. The medium pipe is pushed into the outer sheath (usually polyethylene), so that there is an annular gap between the two pipes. Due to its excellent insulating properties, this annular gap is filled with polyurethane foam. For this purpose, the slightly inclined double tube is provided with end caps, which are equipped with vent holes. Subsequently, the liquid reaction mixture is filled in the annular gap by means of a polyurethane metering which flows down in still liquid form in the pipe gap until the reaction begins. From this time, the further distribution takes place by flowing the slowly rising in viscosity foam until the material is reacted.

Neben der oben beschriebenen Methode gibt es noch weitere Möglichkeiten entsprechende Rohre herzustellen. Ein innovatives Verfahren hierfür stellt die "Lanzentechnik" dar. Hierbei wird der Mischkopf während der Produktion durch den Ringspalt bewegt. Hierfür kann entweder der Mischkopf selbst oder das Rohr bewegt werden. Währenddessen strömt das flüssige PUR-Reaktionsgemisch aus, steigt auf und kann dann das Rohr tragen. Deshalb können bei diesem Verfahren die oben erwähnten Abstandshalter entfallen. Mit dem Lanzenverfahren können Rohre mit einer niedrigeren Schaumdichte bzw. besseren Schaumdichtenverteilung hergestellt werden. Ein weiterer Vorteil ist die Möglichkeit, feinzelligere Schäume einzusetzen, die durch den Einsatz reaktiverer Polyolkomponenten erzielt werden können.In addition to the method described above, there are other ways to produce corresponding pipes. An innovative method for this is the "lance technique". Here, the mixing head is moved through the annular gap during production. For this purpose, either the mixing head itself or the tube can be moved. In the meantime, the liquid PUR reaction mixture flows out, rises and can then carry the pipe. Therefore, in this method, the above-mentioned spacers can be omitted. With the lance method tubes with a lower foam density or better foam density distribution can be produced. Another advantage is the ability to use finer-celled foams that can be achieved through the use of more reactive polyol components.

Beim Lanzenverfahren treten zwei Probleme einzeln oder kombiniert auf: Mangelnde Druckfestigkeiten (Bedingung > 0,3 N/mm2 nach EN 253:2003) und/oder ungenügende Zentrierung des Stahlrohres (Tabelle 7, Koaxialitätstoleranz in Abhängigkeit vom Nennaußendurchmesser, EN 253:2003).In the lancing process, two problems occur individually or in combination: Lack of compressive strength (condition> 0.3 N / mm 2 according to EN 253: 2003) and / or inadequate centering of the steel pipe (Table 7, Coaxiality tolerance as a function of nominal outside diameter, EN 253: 2003) ,

Aufgabe der Erfindung war es daher, ein Polyurethansystem bereitzustellen, welches vorteilhaft bei der Herstellung von gedämmten Rohren verwendet werden kann und dort zu einem Polyurethanschaumstoff mit sehr guter Druckfestigkeit (> 0,3 N/mm2 nach EN 253) führt, mit dem eine hervorragende Zentrierung des Stahlrohres (Mediumrohrs) ermöglicht wird.The object of the invention was therefore to provide a polyurethane system which can be advantageously used in the production of insulated pipes and there leads to a polyurethane foam with very good compressive strength (> 0.3 N / mm 2 according to EN 253), with an excellent Centering of the steel pipe (medium pipe) is made possible.

Die Aufgaben konnten durch die eingangs dargestellten gedämmten Rohre sowie das eingangs beschriebene Verfahren gelöst werden.The tasks could be solved by the insulated tubes shown at the beginning and the method described above.

Durch den Einsatz dieser erfindungsgemäßen Polyole konnte erreicht werden, dass der während des Schäumprozesses aufsteigende Schaum durch die geringere Grundviskosität und den langsameren Anstieg der Reaktionsviskosität das Mediumrohr nur wenig aufschwimmen lässt.By using these polyols according to the invention it was possible to achieve that the foam rising during the foaming process causes the medium pipe to float only slightly due to the lower intrinsic viscosity and the slower increase in the reaction viscosity.

Die bei der Umsetzung eingesetzte Polyolmischung kann üblicherweise (b1) Polyole, (b2) Katalysatoren sowie gegebenenfalls (b3) chemische Treibmittel, (b4) Vernetzer, (b5) Kettenverlängerungsmittel und/oder (b6) Zusatzstoffe enthalten. Dabei weist die Polyolmischung bestehend aus (b1) Polyole, (b2) Katalysatoren sowie gegebenenfalls (b3) chemische Treibmittel, (b4) Vernetzer, (b5) Kettenverlängerungsmittel und/oder (b6) Zusatzstoffe bevorzugt eine Viskosität von kleiner 3000 mPas, bevorzugt weniger als 2400 mPas, mehr bevorzugt weniger als 2200 mPas, gemessen nach DIN 53019 bei 20°C, auf. Dabei bezieht sich diese Viskositätsangabe auf Polyolmischungen (b), die wie dargestellt keine physikalischen Treibmittel enthalten. Als Untergrenze der Viskosität haben sich Werte von 200 mPas, bevorzugt 400 mPas, besonders bevorzugt 600 mPas, gemessen nach DIN 53019 bei 20°C, als sinnvoll erwiesen.The polyol mixture used in the reaction may usually contain (b1) polyols, (b2) catalysts and optionally (b3) chemical blowing agents, (b4) crosslinking agents, (b5) chain extenders and / or (b6) additives. In this case, the polyol mixture consisting of (b1) polyols, (b2) catalysts and optionally (b3) chemical blowing agents, (b4) crosslinking agents, (b5) chain extenders and / or (b6) additives preferably has a viscosity of less than 3000 mPas, preferably less than 2400 mPas, more preferably less than 2200 mPas, measured according to DIN 53019 at 20 ° C, on. This viscosity specification refers to polyol mixtures (b) which, as shown, contain no physical blowing agents. Values of 200 mPas, preferably 400 mPas, particularly preferably 600 mPas, measured according to DIN 53019 at 20 ° C., have proven to be useful as the lower limit of the viscosity.

Es ist grundsätzlich auch möglich, der Polyolmischung physikalische Treibmittel hinzufügen. Die Zugabe von physikalischem Treibmittel führt jedoch zu einer signifikanten Absenkung der Viskosität. Daher beziehen sich die oben gemachten Angaben zur Viskosität der Polyolmischung (b), auch für den Fall, dass sie physikalische Treibmittel enthält, auf die Viskosität der Polyolmischung (b) ohne Zusatz von physikalischen Treibmitteln.It is also possible in principle to add physical blowing agents to the polyol mixture. However, the addition of physical blowing agent leads to a significant lowering of the viscosity. Therefore, even if it contains physical blowing agents, the viscosity information of the polyol mixture (b) given above refers to the viscosity of the polyol mixture (b) without the addition of physical blowing agents.

Die Ausgangsstoffe werden nachfolgend ausführlich dargestellt:The starting materials are described in detail below:

Als Isocyanatkomponente (a) kommen die üblichen aliphatischen, cycloaliphatischen und insbesondere aromatischen Di- und/oder Polyisocyanate zum Einsatz. Bevorzugt verwendet werden Toluylendiisocyanat (TDI), Diphenylmethandiisocyanat (MDI) und insbesondere Gemische aus Diphenylmethandiisocyanat und Polyphenylenpolymethylenpolyisocyanaten (Roh-MDI). Die Isocyanate können auch modifiziert sein, beispielsweise durch Einbau von Uretdion-, Carbamat-, Isocyanurat-, Carbodiimid-, Allophanat- und insbesondere Urethangruppen. Die Isocyanatkomponente (a) kann auch in Form von Polyisocyanatprepolymeren eingesetzt werden. Diese Prepolymere sind im Stand der Technik bekannt. Die Herstellung erfolgt auf an sich bekannte Weise, indem vorstehend beschriebene Polyisocyanate (a), beispielsweise bei Temperaturen von etwa 80°C, mit Verbindungen mit gegenüber Isocyanaten reaktiven Wasserstoffatomen, bevorzugt mit Polyolen, zu Polyisocyanatprepolymeren umgesetzt werden. Das Polyol-Polyisocyanat-Verhältnis wird im allgemeinen so gewählt, dass der NCO-Gehalt des Prepolymeren 8 bis 25 Gew.-%, vorzugsweise 10 bis 22 Gew.-%, besonders bevorzugt 13 bis 20 Gew.-% beträgt.The isocyanate component (a) used are the customary aliphatic, cycloaliphatic and in particular aromatic di- and / or polyisocyanates. Preferably used are tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI) and in particular mixtures of diphenylmethane diisocyanate and polyphenylene polymethylene polyisocyanates (crude MDI). The isocyanates may also be modified, for example by incorporation of uretdione, carbamate, isocyanurate, carbodiimide, allophanate and in particular urethane groups. The isocyanate component (a) can also be used in the form of polyisocyanate prepolymers. These prepolymers are known in the art. The preparation is carried out in a manner known per se by reacting polyisocyanates (a) described above, for example at temperatures of about 80 ° C., with compounds containing isocyanate-reactive hydrogen atoms, preferably polyols, to form polyisocyanate prepolymers. The polyol-polyisocyanate ratio is generally chosen so that the NCO content of the prepolymer 8 to 25 wt .-%, preferably 10 to 22 wt .-%, particularly preferably 13 to 20 wt .-% is.

Zur Herstellung von Polyurethan-Hartschaumstoffen wird insbesondere Roh-MDI eingesetzt.For the production of rigid polyurethane foams in particular crude MDI is used.

In einer bevorzugten Ausführungsform wird die Isocyanatkomponente (a) so gewählt, dass sie eine Viskosität weniger als 600 mPas, bevorzugt von 100 bis 450, besonders bevorzugt von 120 bis 350, insbesondere von 180 bis 320 mPas, gemessen nach DIN 53019 bei 20°C, aufweist.In a preferred embodiment, the isocyanate component (a) is chosen to have a viscosity of less than 600 mPas, preferably from 100 to 450, especially preferably from 120 to 350, in particular from 180 to 320 mPas, measured according to DIN 53019 at 20 ° C having.

Als Polyole (Bestandteil b1) können zusätzlich den erfindungsgemäßen Polyolen allgemein für diesen Zweck bekannte Polyole zum Einsatz kommen. In Betracht kommen z.B. Verbindungen mit mindestens zwei gegenüber Isocyanat reaktiven Gruppen, das heißt mit mindestens zwei mit Isocyanatgruppen reaktiven Wasserstoffatomen. Beispiele hierfür sind Verbindungen mit OH-Gruppen, SH-Gruppen, NH-Gruppen und/oder NH2-Gruppen.As polyols (component b1), in addition to the polyols according to the invention, polyols known in general for this purpose can be used. For example, compounds having at least two isocyanate-reactive groups, ie having at least two hydrogen atoms reactive with isocyanate groups, are suitable. Examples include compounds with OH groups, SH groups, NH groups and / or NH 2 groups.

Als Polyole (Bestandteil b1) kommen bevorzugt Verbindungen auf Basis von Polyesterolen oder Polyetherolen zum Einsatz. Die Funktionalität der Polyetherole und/oder Polyesterole beträgt im allgemeinen 1,9 bis 8, bevorzugt 2,4 bis 7, besonders bevorzugt 2,9 bis 6.Preferred polyols (component b1) are compounds based on polyesterols or polyetherols. The functionality of the polyetherols and / or polyesterols is generally 1.9 to 8, preferably 2.4 to 7, particularly preferably 2.9 to 6.

Die Polyole (b1) weisen bevorzugt eine Hydroxylzahl von größer als 70 mg KOH/g, bevorzugt größer als 100 mg KOH/g, besonders bevorzugt größer als 120 mg KOH/g auf. Als Obergrenze der Hydroxylzahl hat sich im allgemeinen 1000 mg KOH/g, bevorzugt 900 mg KOH/g, besonders 800 mg KOH/g bewährt.The polyols (b1) preferably have a hydroxyl number of greater than 70 mg KOH / g, preferably greater than 100 mg KOH / g, more preferably greater than 120 mg KOH / g. The upper limit of the hydroxyl number has generally proven to be 1000 mg KOH / g, preferably 900 mg KOH / g, especially 800 mg KOH / g.

Bevorzugt enthält Komponente (b1) Polyetherpolyole, die nach bekannten Verfahren, beispielsweise durch anionische Polymerisation mit Alkalihydroxiden, wie Natrium- oder Kaliumhydroxid oder Alkalialkoholaten, wie Natriummethylat, Natrium- oder Kaliumethylat oder Kaliumisopropylat als Katalysatoren und unter Zusatz mindestens eines Startermoleküls das 2 bis 8, vorzugsweise 3 bis 8 reaktive Wasserstoffatome gebunden enthält, oder durch kationische Polymerisation mit Lewis-Säuren, wie Antimonpentachlorid, Borfluorid-Etherat u.a. oder Bleicherde als Katalysatoren aus einem oder mehreren Alkylenoxiden mit 2 bis 4 Kohlenstoffatomen im Alkylenrest hergestellt werden.Component (b1) preferably comprises polyetherpolyols prepared by known processes, for example by anionic polymerization with alkali metal hydroxides, such as sodium or potassium hydroxide or alkali metal alkoxides, such as sodium methylate, sodium or potassium ethylate or potassium isopropylate as catalysts and with the addition of at least one starter molecule 2 to 8, preferably contains 3 to 8 bonded reactive hydrogen atoms, or by cationic polymerization with Lewis acids, such as antimony pentachloride, boron fluoride etherate, inter alia or bleaching earth are prepared as catalysts from one or more alkylene oxides having 2 to 4 carbon atoms in the alkylene radical.

Geeignete Alkylenoxide sind beispielsweise Tetrahydrofuran, 1,3-Propylenoxid, 1,2- bzw. 2,3-Butylenoxid, Styroloxid und vorzugsweise Ethylenoxid und 1,2-Propylenoxid. Die Alkylenoxide können einzeln, alternierend nacheinander oder als Mischungen verwendet werden.Suitable alkylene oxides are, for example, tetrahydrofuran, 1,3-propylene oxide, 1,2- or 2,3-butylene oxide, styrene oxide and preferably ethylene oxide and 1,2-propylene oxide. The alkylene oxides can be used individually, alternately in succession or as mixtures.

Als Startermoleküle kommen Alkohohle in Betracht, wie beispielsweise Glycerin, Trimethylolpropan (TMP), Pentaerythrit, Saccharose, Sorbit, sowie Amine, wie beispielsweise Methylamin, Ethylamin, Isopropylamin, Butylamin, Benzylamin, Anilin, Toluidin, Toluoldiamin (TDA), Naphtylamin, Ethylendiamin, Diethylentriamin, 4,4'-Methylendianilin, 1,3,-Propandiamin, 1,6-Hexandiamin, Ethanolamin, Diethanolamin, Triethanolamin und ähnliche.As starter molecules are alcohols, such as glycerol, trimethylolpropane (TMP), pentaerythritol, sucrose, sorbitol, and amines such as methylamine, ethylamine, isopropylamine, butylamine, benzylamine, aniline, toluidine, toluene diamine (TDA), naphthylamine, ethylenediamine, Diethylenetriamine, 4,4'-methylenedianiline, 1,3-propanediamine, 1,6-hexanediamine, ethanolamine, diethanolamine, triethanolamine and the like.

Weiterhin können als Startermoleküle Kondensationsprodukte aus Formaldehyd, Phenol und Diethanolamin bzw. Ethanolamin, Formaldehyd, Alkylphenolen und Diethanolamin bzw. Ethanolamin, Formaldehyd, Bisphenol A und Diethanolamin bzw. Ethanolamin, Formaldehyd, Anilin und Diethanolamin bzw. Ethanolamin, Formaldehyd, Kresol und Diethanolamin bzw. Ethanolamin, Formaldehyd, Toluidin und Diethanolamin bzw. Ethanolamin sowie Formaldehyd, Toluoldiamin (TDA) und Diethanolamin bzw. Ethanolamin und ähnliche verwendet werden.Furthermore, as a starter molecules condensation products of formaldehyde, phenol and diethanolamine or ethanolamine, formaldehyde, alkylphenols and diethanolamine or ethanolamine, formaldehyde, bisphenol A and diethanolamine or ethanolamine, formaldehyde, aniline and diethanolamine or ethanolamine, formaldehyde, cresol and diethanolamine or Ethanolamine, formaldehyde, toluidine and diethanolamine or ethanolamine and formaldehyde, toluene diamine (TDA) and diethanolamine or ethanolamine and the like can be used.

Bevorzugt werden als Startermolekül Diethylenglykol,, Glycerin und Pentaerythrit verwendet.Diethylene glycol, glycerol and pentaerythritol are preferably used as the starter molecule.

Die Polyolmischung kann optional als Bestandteil (b2) Katalysatoren enthalten. Als Katalysatoren (b2) werden üblicherweise Verbindungen verwendet, welche die PUR- und/oder PIR-Reaktion beschleunigen.The polyol mixture may optionally contain catalysts as component (b2). The catalysts (b2) used are usually compounds which accelerate the PUR and / or PIR reaction.

In Betracht kommen bevorzugt organische Zinnverbindungen, wie Zinn-(II)-salze von organischen Carbonsäuren, und/oder basischen Aminverbindungen, bevorzugt tertiäre Amine, wie beispielsweise Triethylamin, und/oder 1,4-Diaza-bicyclo-(2,2,2)-octan. Die Katalysatoren werden im allgemeinen in einer Menge von 0,001 bis 5 Gew.-%, insbesondere von 0,05 bis 3,5 Gew.-% Katalysator, bezogen auf das Gewicht der Komponente (b), eingesetzt.Preference is given to organic tin compounds, such as tin (II) salts of organic carboxylic acids, and / or basic amine compounds, preferably tertiary amines, such as triethylamine, and / or 1,4-diaza-bicyclo- (2,2,2 ) octane. The catalysts are generally used in an amount of 0.001 to 5 wt .-%, in particular from 0.05 to 3.5 wt .-% catalyst, based on the weight of component (b).

Bevorzugt wird man vor der Umsetzung der Isocyanatkomponente (a) mit der Polyolmischung (b) Glycin, N-((2-Hydroxy-5-nonylphenyl)methyl)-N-methyl-mononatrium Salz (CAS-Nummer 56968-08-2) in die Polyolmischung (b) mischen, besonders bevorzugt zwischen 0,01 und 3,5 Gew.-% Glycin, N-((2-Hydroxy-5-nonylphenyl)methyl)-N-methyl-mononatrium Salz (CAS-Nummer 56968-08-2) in die Polyolmischung (b) mischen, wobei sich die Gewichtsangaben auf das Gesamtgewicht der Polyolmischung (b) enthaltend Glycin, N-((2-Hydroxy-5-nonylphenyl)methyl)-N-methyl-mononatrium Salz (CAS-Nummer 56968-08-2) bezieht.Preference is given, before the reaction of the isocyanate component (a) with the polyol mixture (b), to glycine, N - ((2-hydroxy-5-nonylphenyl) methyl) -N-methylmonosodium salt (CAS No. 56968-08-2) in the polyol mixture (b), more preferably between 0.01 and 3.5 wt .-% glycine, N - ((2-hydroxy-5-nonylphenyl) methyl) -N-methyl-monosodium salt (CAS number 56968 -08-2) in the polyol mixture (b), wherein the weights are based on the total weight of the polyol mixture (b) containing glycine, N - ((2-hydroxy-5-nonylphenyl) methyl) -N-methyl-monosodium salt ( CAS number 56968-08-2).

In dieser Schrift gilt im Zweifel die CAS-Nummer als eindeutige chemische Bezeichnung.In this document, the CAS number is considered to be a clear chemical name in case of doubt.

Bevorzugt wird zusätzlich zu Glycin, N-((2-Hydroxy-5-nonylphenyl)methyl)-N-methyl-mononatrium Salz (CAS-Nummer 56968-08-2) als Katalysator (b2) auch (2-Hydroxypropyl)trimethylammonium-2-ethylhexanoat (CAS-Nummer 62314-22-1), 1-Propan-ammonium-2-hydroxy-N,N,N-trimethyl-formiat, Trimethylhydroxypropylammoniumformiat , 2-((2-Dimethylamino)ethyl)methylamino)ethanol (CAS-Nummer 2212-32-0) und/oder N,N',N"-Tris(dimethylamino-propyl)hexahydrotriazin (CAS-Nummer 15875-13-5) eingesetzt.Preference is given in addition to glycine, N - ((2-hydroxy-5-nonylphenyl) methyl) -N-methyl-monosodium salt (CAS number 56968-08-2) as catalyst (b2) also (2-hydroxypropyl) trimethylammonium 2-ethylhexanoate (CAS number 62314-22-1), 1-propane-ammonium-2-hydroxy-N, N, N-trimethyl-formate, trimethylhydroxypropylammonium formate, 2 - ((2-dimethylamino) ethyl) methylamino) ethanol ( CAS number 2212-32-0) and / or N, N ', N "-tris (dimethylamino-propyl) hexahydrotriazine (CAS number 15875-13-5).

Besonders bevorzugt wird man vor der Umsetzung der Isocyanatkomponente (a) mit der Polyolmischung (b) zwischen 0,01 und 3,5 Gew.-% N,N',N"-Tris(dimethylaminopropyl)hexahydrotriazin (CAS-Nummer 15875-13-5) in die Polyolmischung (b) mischen, wobei sich die Gewichtsangaben auf das Gesamtgewicht der Polyolmischung (b) enthaltend N,N',N"-Tris(dimethylamino-propyl)hexahydrotriazin bezieht.Particularly preferred before the reaction of the isocyanate component (a) with the polyol mixture (b) is between 0.01 and 3.5 wt .-% N, N ', N "-Tris (dimethylaminopropyl) hexahydrotriazine (CAS number 15875-13 5) in the polyol mixture (b), wherein the weights are based on the total weight of the polyol mixture (b) containing N, N ', N "-Tris (dimethylamino-propyl) hexahydrotriazine.

Besonders bevorzugt ist ferner, dass man zusätzlich zu Glycin, N-((2-Hydroxy-5-nonylphenyl)methyl)-N-methyl-mononatrium Salz (CAS-Nummer 56968-08-2) als Katalysator (b2) auch Dimethylcyclohexylamin (CAS-Nummer 98-94-2) einsetzt.It is further particularly preferred that in addition to glycine, N - ((2-hydroxy-5-nonylphenyl) methyl) -N-methyl-monosodium salt (CAS number 56968-08-2) as catalyst (b2) also dimethylcyclohexylamine ( CAS number 98-94-2).

Besonders bevorzugt wird man vor der Umsetzung der Isocyanatkomponente (a) mit der Polyolmischung (b) zwischen 0,01 und 3,5 Gew.-% Dimethylcyclohexylamin in die Polyolmischung (b) mischen, wobei sich die Gewichtsangaben auf das Gesamtgewicht der Polyolmischung (b) enthaltend Dimethylcyclohexylamin bezieht.It is particularly preferred to mix between 0.01 and 3.5% by weight of dimethylcyclohexylamine in the polyol mixture (b) before reacting the isocyanate component (a) with the polyol mixture (b), the weight data being based on the total weight of the polyol mixture (b ) containing dimethylcyclohexylamine.

Besonders wird man zusätzlich zu Glycin, N-((2-Hydroxy-5-nonylphenyl)methyl)-N-methyl-mononatrium Salz (CAS-Nummer 56968-08-2) als Katalysator (b2) auch Methylbis(2-dimethylaminoethyl)amin (CAS-Nummer 3030-47-5) und/oder N,N,N',N'-tetramethyl-2,2'oxybis(ethylamin) (CAS-Nummer 3033-62-3) einsetzen. Besonders bevorzugt wird man vor der Umsetzung der Isocyanatkomponente (a) mit der Polyolmischung (b) zwischen 0,01 und 3,5 Gew.-% Methylbis(2-dimethylaminoethyl)amin (CAS-Nummer 3030-47-5) und/oder N,N,N',N'-tetramethyl-2,2'oxybis(ethylamin) (CAS-Nummer 3033-62-3) in die Polyolmischung (b) mischen, wobei sich die Gewichtsangaben auf das Gesamtgewicht der Polyolmischung (b) enthaltend Methylbis(2-dimethylaminoethyl)amin (CAS-Nummer 3030-47-5) und/oder N,N,N',N'-tetramethyl-2,2'oxybis-(ethylamin) (CAS-Nummer 3033-62-3) bezieht.In particular, in addition to glycine, N - ((2-hydroxy-5-nonylphenyl) methyl) -N-methyl-monosodium salt (CAS number 56968-08-2) as catalyst (b2) also methylbis (2-dimethylaminoethyl) amine (CAS number 3030-47-5) and / or N, N, N ', N'-tetramethyl-2,2'oxybis (ethylamine) (CAS number 3033-62-3). Particularly preferred is before the reaction of the isocyanate component (a) with the polyol mixture (b) between 0.01 and 3.5 wt .-% methylbis (2-dimethylaminoethyl) amine (CAS number 3030-47-5) and / or N, N, N ', N'-tetramethyl-2,2'-oxybis (ethylamine) (CAS number 3033-62-3) in the polyol mixture (b), wherein the weights are based on the total weight of the polyol mixture (b) containing methylbis (2-dimethylaminoethyl) amine (CAS number 3030-47-5) and / or N, N, N ', N'-tetramethyl-2,2'oxybis- (ethylamine) (CAS number 3033-62- 3) relates.

Die Polyolmischung kann ferner optional als Bestandteil (b3) chemische Treibmittel enthalten. Als chemische Treibmittel sind Wasser oder Carbonsäuren, insbesondere Ameisensäure als chemisches Treibmittel bevorzugt. Das chemische Treibmittel wird im allgemeinen in einer Menge von 0,1 bis 5 Gew.-%, insbesondere von 0,5 bis 3,0 Gew.-%, bezogen auf das Gewicht der Komponente (b), eingesetzt.The polyol mixture may further optionally contain as component (b3) chemical blowing agents. As chemical blowing agents, water or carboxylic acids, especially formic acid, are preferred as the chemical blowing agent. The chemical blowing agent is generally used in an amount of 0.1 to 5 wt .-%, in particular from 0.5 to 3.0 wt .-%, based on the weight of component (b).

Wie vorstehend erwähnt kann die Polyolmischung physikalisches Treibmittel enthalten. Darunter versteht man Verbindungen, die in den Einsatzstoffen der Polyurethan-Herstellung gelöst oder emulgiert sind und unter den Bedingungen der Polyurethanbildung verdampfen. Dabei handelt es sich beispielsweise um Kohlenwasserstoffe, halogenierte Kohlenwasserstoffe, und andere Verbindungen, wie zum Beispiel perfluorierte Alkane, wie Perfluorhexan, Fluorchlorkohlenwasserstoffe, sowie Ether, Ester, Ketone und/oder Acetale. Diese werden üblicherweise in einer Menge von 1 bis 30 Gew.-%, bevorzugt 2 bis 25 Gew.-%, besonders bevorzugt 3 bis 20 Gew.-%, bezogen auf das Gesamtgewicht der Komponenten b) eingesetzt.As mentioned above, the polyol mixture may contain physical blowing agent. This refers to compounds which are dissolved or emulsified in the starting materials of polyurethane production and evaporate under the conditions of polyurethane formation. These are, for example, hydrocarbons, halogenated hydrocarbons, and other compounds, such as perfluorinated alkanes, such as perfluorohexane, chlorofluorocarbons, and ethers, esters, ketones and / or acetals. These are usually used in an amount of 1 to 30 wt .-%, preferably 2 to 25 wt .-%, particularly preferably 3 to 20 wt .-%, based on the total weight of components b).

In einer bevorzugten Ausführungsform enthält die Polyolmischung (b) als Bestandteil (b4) Vernetzer. Unter Vernetzer werden Verbindungen verstanden, die ein Molekulargewicht von 60 bis weniger als 400 g/mol aufweisen und mindestens 3 gegenüber Isocyanaten reaktive Wasserstoffatome aufweisen. Ein Beispiel hierfür ist Glycerin.In a preferred embodiment, the polyol mixture (b) contains crosslinker as component (b4). Crosslinkers are understood as meaning compounds which have a molecular weight of 60 to less than 400 g / mol and have at least 3 isocyanate-reactive hydrogen atoms. An example of this is glycerin.

Die Vernetzer werden im allgemeinen in einer Menge von 1 bis 10 Gew.-%, bevorzugt von 2 bis 6 Gew.-%, bezogen auf das Gesamtgewicht der Polyolmischung (b) (jedoch ohne physikalische Treibmittel), eingesetzt.The crosslinkers are generally used in an amount of from 1 to 10% by weight, preferably from 2 to 6% by weight, based on the total weight of the polyol mixture (b) (but without physical blowing agents).

In einer weiteren bevorzugten Ausführungsform enthält die Polyolmischung (b) als Bestandteil (b5) Kettenverlängerungsmittel, die der Erhöhung der Vernetzungsdichte dienen. Unter Kettenverlängerungsmittel werden Verbindungen verstanden, die ein Molekulargewicht von 60 bis weniger als 400 g/mol aufweisen und 2 gegenüber Isocyanaten reaktive Wasserstoffatome aufweisen. Beispiele hierfür sind Butandiol, Diethylenglykol, Dipropylenglykol sowie Ethylenglykol.In a further preferred embodiment, the polyol mixture (b) contains, as constituent (b5), chain extenders which serve to increase the crosslinking density. Chain extenders are understood as meaning compounds which have a molecular weight of 60 to less than 400 g / mol and have 2 isocyanate-reactive hydrogen atoms. Examples of these are butanediol, diethylene glycol, dipropylene glycol and ethylene glycol.

Die Kettenverlängerungsmittel werden im allgemeinen in einer Menge von 2 bis 20 Gew.-%, bevorzugt von 4 bis 15 Gew.-%, bezogen auf das Gesamtgewicht der Polyolmischung (b) (jedoch ohne physikalische Treibmittel), eingesetzt.The chain extenders are generally used in an amount of from 2 to 20% by weight, preferably from 4 to 15% by weight, based on the total weight of the polyol mixture (b) (but without physical blowing agents).

Die Komponenten (b4) und (b5) können in der Polyolmischung einzeln oder in Kombination eingesetzt werden.The components (b4) and (b5) can be used in the polyol mixture individually or in combination.

Durch Umsetzung des erfindungsgemäßen Polyurethansystems sind die erfindungsgemäßen Polyurethanschaumstoffe erhältlich. Bei der Umsetzung werden die Polyisocyanate (a) und die Polyolmischung (b) im allgemeinen in solchen Mengen zur Umsetzung gebracht, dass die Isocyanat-Kennzahl des Schaums 90 bis 250, bevorzugt 100 bis 200 beträgt.The polyurethane foams according to the invention are obtainable by reacting the polyurethane system according to the invention. In the reaction, the polyisocyanates (a) and the polyol mixture (b) are generally reacted in amounts such that the isocyanate index of the foam is 90 to 250, preferably 100 to 200.

In einer bevorzugten Ausführungsform werden die Komponenten (a) und (b) des Polyurethansystems so gewählt werden, dass der resultierende Schaumstoff eine Druckfestigkeit (bei Rohdichte 60 kg/m3) von größer 0,25 N/mm2, bevorzugt größer 0,28 N/mm2, besonders bevorzugt größer 0,30 N/mm2, gemessen nach DIN 53421, aufweist.In a preferred embodiment, the components (a) and (b) of the polyurethane system are chosen so that the resulting foam a compressive strength (density 60 kg / m 3 ) of greater than 0.25 N / mm 2 , preferably greater than 0.28 N / mm 2 , more preferably greater than 0.30 N / mm 2 , measured according to DIN 53421.

Dem erfindungsgemäßen Polyurethansystem können gegebenenfalls auch noch Zusatzstoffe (b6) einverleibt werden. Unter Zusatzstoffe (b6) werden die im Stand der Technik bekannten und üblichen Hilfs- und Zusatzstoffe verstanden, jedoch ohne physikalische Treibmittel. Genannt seien beispielsweise oberflächenaktive Substanzen, Schaumstabilisatoren, Zellregler, Füllstoffe, Farbstoffe, Pigmente, Flammschutzmittel, Antistatika, Hydrolyseschutzmittel und/oder fungistatisch und bakteriostatisch wirkende Substanzen. Anzumerken ist, dass die oben angegebenen bevorzugten Viskositätsbereiche der Komponente (b) sich auf eine Polyolmischung (b) inklusive gegebenenfalls zugesetzter Zusatzstoffe (b6) (aber exklusive gegebenenfalls zugesetztem physikalischem Treibmittel) beziehen.If appropriate, additives (b6) can also be incorporated into the polyurethane system according to the invention. Additives (b6) are understood to be the auxiliaries and additives known and customary in the prior art, but without physical blowing agents. Mention may be made, for example, of surface-active substances, foam stabilizers, cell regulators, fillers, dyes, pigments, flame retardants, antistatic agents, hydrolysis protectants and / or fungistatic and bacteriostatic agents Substances. It should be noted that the preferred viscosity ranges of component (b) given above relate to a polyol mixture (b) including any added additives (b6) (but excluding any added physical blowing agent).

Die erfindungsgemäßen Polyurethansysteme finden bevorzugt zur Herstellung von gedämmten Rohren, beispielsweise von Fernwärmerohren, Anwendung. Gegenstand der Erfindung ist somit die Verwendung des erfindungsgemäßen Polyurethansystems zur Herstellung von gedämmten Rohren.The polyurethane systems according to the invention are preferably used for producing insulated pipes, for example district heating pipes. The invention thus relates to the use of the polyurethane system according to the invention for the production of insulated pipes.

In einer bevorzugten Ausführungsform wird das erfindungsgemäße Polyurethansystem zur Herstellung von gedämmten Verbundmantelrohre für erdverlegte Fernwärmenetze gemäß DIN EN 253 verwendet.In a preferred embodiment, the polyurethane system according to the invention for the production of insulated composite jacketed pipes for buried district heating networks according to DIN EN 253 is used.

Weiterhin ist Gegenstand der Erfindung ein gedämmtes Rohr für erdverlegte Fernwärmenetze, aufgebaut aus

  1. i) einem Mediumrohr
  2. ii) einer Schicht aus Dämmmaterial, enthaltend den erfindungsgemäßen Polyurethanschaumstoff, und
  3. iii) einem Mantelrohr.
Furthermore, the subject of the invention is an insulated pipe for buried district heating networks, constructed from
  1. i) a medium pipe
  2. ii) a layer of insulating material containing the polyurethane foam according to the invention, and
  3. iii) a jacket pipe.

Bei dem Mediumrohr (i) handelt es sich im allgemeinen um ein Stahlrohr mit einem Außendurchmesser von 1 bis 120 cm, bevorzugt 4 bis 110 cm und einer Länge von 1 bis 24 Meter, bevorzugt 6 bis 16 Meter.The medium pipe (i) is generally a steel pipe having an outer diameter of 1 to 120 cm, preferably 4 to 110 cm and a length of 1 to 24 meters, preferably 6 to 16 meters.

Auf der Außenseite des Mediumrohres angeordnet ist eine Schicht aus Dämmmaterial (ii), enthaltend den erfindungsgemäßen Polyurethanschaumstoff. Diese Schicht weist im allgemeinen eine Dicke von 1 bis 20 cm, bevorzugt 2 bis 10 cm auf.Arranged on the outside of the medium pipe is a layer of insulating material (ii) containing the polyurethane foam according to the invention. This layer generally has a thickness of 1 to 20 cm, preferably 2 to 10 cm.

In einer bevorzugten Ausführungsform weist die Schicht aus Dämmmaterial eine Gesamtrohdichte von 55 bis 100 kg/m3, bevorzugt von 60 bis 75 kg/m3, besonders bevorzugt von 60 bis 67 kg/m3 auf. Unter Gesamtrohdichte ist hier die Rohdichteverteilung über den Rohrquerschnitt und die Rohrlänge gemeint.In a preferred embodiment, the layer of insulating material has a total apparent density of 55 to 100 kg / m 3 , preferably from 60 to 75 kg / m 3 , particularly preferably from 60 to 67 kg / m 3 . Total gross density refers here to the raw density distribution over the pipe cross-section and the pipe length.

Bevorzugt wird man die Umsetzung der Isocyanatkomponente mit der Polyolkomponente bei einer Verdichtung von größer 1,1 durchführen. Unter Verdichtung versteht man den Quotienten aus der Gesamtfülldichte des Rohrspaltes dividiert durch die freigeschäumte Kernrohdichte bestimmt an einem unverdichteten Schaumkörper.It is preferred to carry out the reaction of the isocyanate component with the polyol component at a compression of greater than 1.1. Compression is the quotient of the total filling density of the pipe gap divided by the free-blown core raw density determined on an uncompressed foam body.

Diese Verdichtung kann dadurch erreicht werden, dass man die Reaktionsprofil des Schaumes so einstellt, dass der frische Schaum den bereits eingefüllten Schaum verdichtet. Anders ausgedrückt verdichtet der Schaum von innen heraus. Diese Verdichtung bietet den Vorteil, dass höhere Druckfestigkeiten sowie ein verbesserte Zentrierung des Mediumrohres erreicht werden können.This densification can be achieved by adjusting the reaction profile of the foam so that the fresh foam compresses the already filled foam. In other words, the foam compresses from the inside out. This compaction offers the advantage that higher compressive strengths and improved centering of the carrier pipe can be achieved.

In einer weiteren bevorzugten Ausführungsform weist die Schicht aus Dämmmaterial (ii), enthaltend den erfindungsgemäßen Polyurethanschaumstoff eine Wärmeleitfähigkeit von weniger als 27 mW/mK, bevorzugt von 20 bis 26,0, besonders bevorzugt 20 bis 24 gemessen nach EN ISO 8497 auf.In a further preferred embodiment, the layer of insulating material (ii) containing the polyurethane foam of the invention has a thermal conductivity of less than 27 mW / mK, preferably from 20 to 26.0, particularly preferably 20 to 24 measured according to EN ISO 8497.

Das Mantelrohr (iii) umgibt die Schicht aus Dämmmaterial und besteht im allgemeinen aus Kunststoff, beispielsweise aus Polyethylen, und weist üblicherweise eine Dicke von 1 bis 30 mm auf. Der Innendurchmesser des Mantelrohrs beträgt im allgemeinen 6 bis 140 cm, bevorzugt 10 bis 120 cm.The jacket tube (iii) surrounds the layer of insulating material and is generally made of plastic, such as polyethylene, and usually has a thickness of 1 to 30 mm. The inner diameter of the jacket tube is generally 6 to 140 cm, preferably 10 to 120 cm.

Das Mantelrohr (iii) kann gegebenenfalls aus mehreren Schichten bestehen, die beim Extrusionsvorgang zusammengeführt werden. Ein Beispiel hierfür ist das Einbringen von mehrlagigen Folien zwischen PUR-Schaumstoff und PE-Mantel, wobei die Folie zur Verbesserung der Sperrwirkung mindestens eine metallische Lage enthält. Geeignete Mantelrohre dieses Typs sind in EP-A-960 723 beschrieben.The jacket tube (iii) may optionally consist of several layers, which are merged during the extrusion process. An example of this is the introduction of multilayer films between PUR foam and PE sheath, wherein the film contains at least one metallic layer to improve the barrier effect. Suitable jacket tubes of this type are in EP-A-960 723 described.

In einer besonders bevorzugten Ausführungsform handelt es sich bei dem gedämmten Rohr um ein gedämmtes Verbundmantelrohr für erdverlegte Fernwärmenetze, welches die Anforderungen von DIN EN 253 erfüllt.In a particularly preferred embodiment, the insulated pipe is an insulated composite casing pipe for buried district heating networks, which meets the requirements of DIN EN 253.

Bevorzugt wird man die Isocyanatkomponente (a) und die Polyolmischung (b) mittels eines Mischkopfes, der axial zwischen Mantelrohr und Mediumrohr bewegt wird, eintragen. Dabei dient der Mischkopf während des Schäumvorganges bevorzugt als Abstandshalter zwischen Mediumrohr und Mantelrohr.Preferably, the isocyanate component (a) and the polyol mixture (b) by means of a mixing head, which is moved axially between the casing pipe and medium pipe, enter. During the foaming process, the mixing head preferably serves as a spacer between carrier pipe and casing pipe.

Bevorzugt erfolgt die Herstellung der erfindungsgemäßen Rohre mittels der Lanzentechnik, die beispielhaft in der Figur 1 dargestellt wird. In der Figur 1 haben die Zahlen die folgende Bedeutung:

  • 1: Dichtring
  • 2: Schelle
  • 3: Endkappe
  • 5: Mantelrohr
  • 6: Führungsring
  • 7: Mischkopf
  • 8: Mediumrohr
  • 9: Verschlussdeckel
  • 10: PU-Schäumanlage
Preferably, the production of the tubes according to the invention by means of the lance technique, which is exemplified in the FIG. 1 is pictured. In the FIG. 1 the numbers have the following meaning:
  • 1: sealing ring
  • 2: clamp
  • 3: end cap
  • 5: jacket pipe
  • 6: Guide ring
  • 7: mixing head
  • 8: Medium pipe
  • 9: cap
  • 10: PU foaming system

In einem Verfahren gemäß Figur 1 handelt es sich um ein diskontinuierliches Verfahren. Im Rahmen dieses Verfahrens wird zwischen dem Mediumrohr (in der Regel Stahl) und dem äußeren Mantelrohr (in der Regel Polyethylen) ein Führungsring mit dem Mischkopf geschoben, der axial beweglich ist und zudem als Abstandshalter zwischen Mediumrohr und Mantelrohr dient. Der Ringspalt zwischen Mediumrohr und Mantelrohr wird aufgrund seiner guten Dämmeigenschaften mit Polyurethanschaumstoff gefüllt. Das Befüllen in den Ringspalt erfolgt bevorzugt mittels einer Polyurethandosiermaschine, die das flüssige Reaktionsgemisch über den Mischkopf in noch flüssiger Form einträgt.In a method according to FIG. 1 it is a discontinuous process. As part of this process, a guide ring is pushed with the mixing head between the medium pipe (usually steel) and the outer jacket tube (usually polyethylene), which is axially movable and also serves as a spacer between the carrier pipe and casing pipe. The annular gap between medium pipe and casing pipe is filled with polyurethane foam due to its good insulating properties. The filling in the annular gap is preferably carried out by means of a polyurethane metering machine, which enters the liquid reaction mixture via the mixing head in still liquid form.

Der Einsatz des erfindungsgemäßen Polyurethansystems führt im erfindungsgemäßen Verfahren zur Herstellung gedämmter Rohre zu folgenden Vorteilen:The use of the polyurethane system according to the invention leads to the following advantages in the process according to the invention for producing insulated pipes:

Es können Druckfestigkeiten erzielt werden, die oberhalb von 0,25 N/mm2 liegen. Idealerweise werden Rohre hergestellt, die Druckfestigkeiten > 0,3 N/mm2 besitzen und der EN 253 entsprechen.Compressive strengths can be achieved which are above 0.25 N / mm 2 . Ideally, tubes are produced which have compressive strengths> 0.3 N / mm 2 and correspond to EN 253.

Mit dem erfindungsgemäßen Polyurethanschaumstoff können gedämmte Rohre mit einer Zentrierung des Mediumrohres erzielt werden, die die Anforderungen nach Tabelle 7 - Koaxialitätstoleranz in Abhängigkeit vom Nennaußendurchmesser, EN 253:2003 erfüllenWith the polyurethane foam according to the invention insulated pipes can be achieved with a centering of the carrier pipe, which meet the requirements of Table 7 - Coaxiality tolerance depending on the nominal outside diameter, EN 253: 2003

Beispiele:Examples:

Die in der Tabelle 1 dargestellten Rezepturen wurden verschäumt. Die Produkteigenschaften sind ebenfalls in der Tabelle 1 dargestellt. Tabelle 1: Beispiel 1 2 3 4 Polyol A 40 - 40 - Polyol B 44,8 44,8 45,8 45,8 Polyol C 10 10 10 10 Polyol D - 40 - 40 Tegostab® B 8467 1,5 1,5 1,5 1,5 Kat 1 0,8 0,8 0,8 0,8 Kat 2 0,2 0,2 0,2 0,2 Kat 3 0,7 0,7 0,7 0,7 Kat 4 1,0 1,0 - - Wasser 1,0 1,0 1,0 1,0 Summe 100,0 100,0 100,0 100,0 Pentan 6,0 6,0 6,0 6,0 Lupranat® M 20S 132 132 132 132 Isocyanat-Index 130 130 130 130 Viskosität [mPa*s] 2800 4200 2800 4200 Zentrierung-Abweichung (D=125 mm)** 2 mm 3 mm 2 mm 10 mm Druckfestigkeit*** 0,42 N/mm2 0,40 N/mm2 0,34 N/mm2 0,25 N/mm2 Verdichtungsfaktor 1,2 1,15 1,1 1,05 OH-Zahl Funktionalität Viskosität [25°C] MG [g/mol] Polyol A 403 mg KOH/g 3,9 2200 550 Polyol B 405 mg KOH/g 3,8 17000 530 Polyol C 400 mg KOH/g 3 370 420 Polyol D 490 mg KOH/g 4,3 8300 500 ** EN 253 Prüfkriterium ist Außendurchmesserabhängig, erfüllt bei s = 3 mm (D=75 - 160 mm)
*** EN 253 erfüllt, bei Druckfestigkeiten >= 0,3 N/mm2

Polyol A:
gestartet mit Saccharose, Pentaerythrit und Diethylenglykol
Polyol B:
gestartet mit TDA, alkoxyliert mit EO und PO
Polyol C:
gestartet mit Glycerin, alkoxyliert mit PO
Polyol D:
gestartet mit Sorbitol, alkoxyliert mit PO
Kat 1:
Dimethylcyclohexylamin (CAS-Nummer 98-94-2)
Kat 2:
Lupragen® N 600 (BASF Aktiengesellschaft), N,N',N"-Tris(dimethylaminopropyl)hexahydrotriazin (CAS-Nummer 15875-13-5)
Kat 3:
Lupragen® N 301 (BASF Aktiengesellschaft) Methylbis(2-dimethylaminoethyl)amin (CAS-Nummer 3030-47-5)
Kat 4:
Dabco® Curithane® 52, enthält Glycin, N-((2-Hydroxy-5-nonylphenyl)methyl)-N-methyl-mononatrium Salz (CAS-Nummer 56968-08-2) Lupranat® M20S (BASF Aktiengesellschaft): MDI
The formulations shown in Table 1 were foamed. The product properties are also shown in Table 1. Table 1: example 1 2 3 4 Polyol A 40 - 40 - Polyol B 44.8 44.8 45.8 45.8 Polyol C 10 10 10 10 Polyol D - 40 - 40 Tegostab® B 8467 1.5 1.5 1.5 1.5 Cat 1 0.8 0.8 0.8 0.8 Cat 2 0.2 0.2 0.2 0.2 Cat 3 0.7 0.7 0.7 0.7 Cat 4 1.0 1.0 - - water 1.0 1.0 1.0 1.0 total 100.0 100.0 100.0 100.0 pentane 6.0 6.0 6.0 6.0 Lupranat® M 20S 132 132 132 132 Isocyanate index 130 130 130 130 Viscosity [mPa * s] 2800 4200 2800 4200 Centering deviation (D = 125 mm) ** 2 mm 3 mm 2 mm 10 mm Compressive strength *** 0.42 N / mm 2 0.40 N / mm 2 0.34 N / mm 2 0.25 N / mm 2 compression factor 1.2 1.15 1.1 1.05 OH number functionality Viscosity [25 ° C] MG [g / mol] Polyol A 403 mg KOH / g 3.9 2200 550 Polyol B 405 mg KOH / g 3.8 17000 530 Polyol C 400 mg KOH / g 3 370 420 Polyol D 490 mg KOH / g 4.3 8300 500 ** EN 253 Test criterion is external diameter dependent, fulfilled at s = 3 mm (D = 75 - 160 mm)
*** EN 253, with compressive strengths> = 0.3 N / mm 2
Polyol A:
started with sucrose, pentaerythritol and diethylene glycol
Polyol B:
started with TDA, alkoxylated with EO and PO
Polyol C:
started with glycerol, alkoxylated with PO
Polyol D:
started with sorbitol, alkoxylated with PO
Cat 1:
Dimethylcyclohexylamine (CAS number 98-94-2)
Cat 2:
Lupragen® N 600 (BASF Aktiengesellschaft), N, N ', N "-tris (dimethylaminopropyl) hexahydrotriazine (CAS number 15875-13-5)
Cat 3:
Lupragen® N 301 (BASF Aktiengesellschaft) Methyl bis (2-dimethylaminoethyl) amine (CAS number 3030-47-5)
Cat 4:
Dabco® Curithane® 52, contains glycine, N - ((2-hydroxy-5-nonylphenyl) methyl) -N-methyl-monosodium salt (CAS number 56968-08-2) Lupranat® M20S (BASF Aktiengesellschaft): MDI

Vergleicht man die Druckfestigkeiten der vier verschiedenen Rezepturen, so erkennt man, dass sich das erfindungsgemäße Polyol A (Beispiele 1 und 3) deutlich positiv auswirkt. Gegenüber der Standardrezeptur konnte der Grenzwert der EN 253 von 0,3 N/mm2 übersprungen werden. Die Zentrierung des Mediumrohres kann ebenfalls deutlich durch das Polyol verbessert werden und liegt bei der geprüften Rohrdimension von 60,3/125mm unterhalb der Grenze von 3mm. Die Zugabe des bevorzugten Katalysators (Curithane 52, Beispiele 1 und 2) führt zu einer deutlichen Verbesserung der Druckfestigkeit gegenüber der Standardrezeptur und einer Zentrierung, die verbessert ist, aber die EN 253 nur knapp erreicht. Beide Merkmale zusammen führen zu verbessernden Eigenschaften des gedämmten Rohres und somit zu deutlichen Vorteilen und einem sicheren Überschreiten der Grenzwerte der EN 235:2003.Comparing the compressive strengths of the four different formulations, it can be seen that the inventive polyol A (Examples 1 and 3) has a clearly positive effect. Compared to the standard formula, the limit of EN 253 of 0.3 N / mm 2 could be skipped. The centering of the medium pipe can also be significantly improved by the polyol and is in the tested pipe dimension of 60.3 / 125mm below the limit of 3mm. The addition of the preferred catalyst (Curithane 52, Examples 1 and 2) leads to a significant improvement in the compressive strength compared to the standard formulation and a centering, which is improved, but the EN 253 barely reached. Both characteristics together lead to improved properties of the insulated pipe and thus to clear advantages and safe exceeding of the limit values of EN 235: 2003.

Claims (8)

  1. An insulated pipe comprising
    i) pipe for a medium,
    ii) polyurethane foam obtainable by reaction of an isocyanate component (a) with a polyol mixture (b) and
    iii) outer pipe,
    wherein the polyol mixture (b) comprises at least one polyether polyalcohol (b1i) which is obtainable by alkoxylation of sucrose and diethylene glycol and, if appropriate, pentaerythritol and/or glycerol with ethylene oxide and/or propylene oxide and has a functionality toward isocyanates of greater than 3, a hydroxyl number of greater than 300 mg KOH/g and a viscosity of less than 2500 mPas, measured in accordance with DIN 53019 at 25°C.
  2. A process for producing insulated pipes, which comprises the steps:
    1) provision of the pipe for a medium and the outer pipe, with the pipe for a medium being located within the outer pipe,
    2) production of a polyurethane foam by reaction of an isocyanate component (a) with a polyol mixture (b) between the pipe for a medium and the outer pipe,
    wherein the polyol mixture (b) comprises at least one polyether polyalcohol (b1i) which is obtainable by alkoxylation of sucrose and diethylene glycol and, if appropriate, pentaerythritol and/or glycerol with ethylene oxide and/or propylene oxide and has a functionality toward isocyanates of greater than 3, a hydroxyl number of greater than 300 mg KOH/g and a viscosity of less than 2500 mPas, measured in accordance with DIN 53019 at 25°C.
  3. The process according to claim 2, wherein the polyol mixture comprises (b1) polyols, (b2) catalysts and, if appropriate, (b3) chemical blowing agents, (b4) crosslinkers, (b5) chain extenders and/or (b6) additives.
  4. The process according to claim 2, wherein the polyol mixture comprising (b1) polyols, (b2) catalysts and, if appropriate, (b3) chemical blowing agents, (b4) crosslinkers, (b5) chain extenders and/or (b6) additives has a viscosity of less than 3000 mPas, measured in accordance with DIN 53019 at 20°C.
  5. The process according to claim 2, wherein the reaction is carried out at a compaction of greater than 1.1.
  6. The process according to claim 2, wherein the reaction is carried out at an index of from 100 to 200.
  7. The process according to claim 2, wherein the isocyanate component (a) and the polyol mixture (b) are introduced by means of a mixing head which is moved axially between the outer pipe and the pipe for a medium.
  8. The process according to claim 7, wherein the mixing head serves as spacer between the pipe for a medium and the outer pipe during the foaming procedure.
EP06121729A 2005-10-19 2006-10-04 Polyurethane foams for insulating pipes Active EP1777051B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL06121729T PL1777051T3 (en) 2005-10-19 2006-10-04 Polyurethane foams for insulating pipes

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE102005050413A DE102005050413A1 (en) 2005-10-19 2005-10-19 Polyurethane foams for pipe insulation

Publications (2)

Publication Number Publication Date
EP1777051A1 EP1777051A1 (en) 2007-04-25
EP1777051B1 true EP1777051B1 (en) 2008-07-16

Family

ID=37649351

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06121729A Active EP1777051B1 (en) 2005-10-19 2006-10-04 Polyurethane foams for insulating pipes

Country Status (5)

Country Link
EP (1) EP1777051B1 (en)
AT (1) ATE401181T1 (en)
DE (2) DE102005050413A1 (en)
DK (1) DK1777051T3 (en)
PL (1) PL1777051T3 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014012877A1 (en) 2012-07-17 2014-01-23 Basf Se Method for continuous production of foams in tubes
WO2020201312A1 (en) 2019-04-02 2020-10-08 Basf Se Insulated pipe containing polyurethane foam which is foamed by an environmentally friendly foaming agent and has a low degree of brittleness
US11472152B2 (en) 2017-05-30 2022-10-18 Basf Se Method for producing insulated pipes

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8986801B2 (en) 2011-01-27 2015-03-24 Basf Se Polyurethane having improved insulating properties
CN110421774B (en) * 2018-05-06 2023-11-10 内蒙古君诚兴业管道有限责任公司 Online automatic concentricity poling plugging device and automatic foaming production line
CN112646121A (en) * 2020-12-11 2021-04-13 淄博汇德聚氨酯制品股份有限公司 Polyurethane rigid foam thermal insulation material, and preparation method and application thereof

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4522578A (en) * 1980-12-08 1985-06-11 J-M Manufacturing Co., Inc. Apparatus for introducing a foamable plastic insulation into the space defined by an inner core pipe and an outer casing pipe while maintaining the spacing of the pipes
DE19711068A1 (en) * 1997-03-17 1998-09-24 Basf Ag Process and devices for the production of pipes insulated with foam
DE19817507A1 (en) * 1998-04-20 1999-10-21 Basf Ag Process for the production of rigid polyurethane foams with a reduced thermal conductivity and their use
DE19924771A1 (en) * 1999-05-29 2000-12-21 Buna Sow Leuna Olefinverb Gmbh Production of polyetherpolyol, use for preparing polyurethane without additional catalyst, comprises addition of alkylene oxides to polysaccharides in presence of alkaline catalyst
DE02758190T1 (en) * 2002-09-11 2005-10-20 Star Pipe Fredericia As METHOD AND APPARATUS FOR PRODUCING LENGTHS OF PREISOLATED PIPES

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014012877A1 (en) 2012-07-17 2014-01-23 Basf Se Method for continuous production of foams in tubes
US11472152B2 (en) 2017-05-30 2022-10-18 Basf Se Method for producing insulated pipes
WO2020201312A1 (en) 2019-04-02 2020-10-08 Basf Se Insulated pipe containing polyurethane foam which is foamed by an environmentally friendly foaming agent and has a low degree of brittleness
US11982395B2 (en) 2019-04-02 2024-05-14 Basf Se Insulated pipe containing polyurethane foam which is foamed by an environmentally friendly foaming agent and has a low degree of brittleness

Also Published As

Publication number Publication date
DE502006001116D1 (en) 2008-08-28
DK1777051T3 (en) 2008-11-10
EP1777051A1 (en) 2007-04-25
DE102005050413A1 (en) 2007-04-26
ATE401181T1 (en) 2008-08-15
PL1777051T3 (en) 2008-12-31

Similar Documents

Publication Publication Date Title
EP2134762B1 (en) Insulated pipes
EP1799736B1 (en) Method for producing rigid polyurethane foams
EP2870188B1 (en) Production of foams having improved properties
EP3350242B1 (en) Method for manufacturing a polyurethane polyisocyanurate solid foam
EP3548533B1 (en) Polyurethane hard foams, method for their manufacture and application thereof
EP1777051B1 (en) Polyurethane foams for insulating pipes
EP2526333B1 (en) Polyurethane rigid foam envelope for connection of pipes
EP3368584B1 (en) Polyether ester and use of same for producing polyurethane solid foam materials
EP2786059B1 (en) Method for producing insulated casing pipes in a continuous production process
EP1777242B1 (en) Polyurethane foams for insulating pipes
DE69620850T2 (en) Polyether polyol for the production of rigid polyurethane foams
EP1783152A2 (en) Insulated pipes
EP2111423B2 (en) Polyurethane rigid foams
EP1777244A1 (en) Polyurethane foams for insulating pipes
EP2931773B1 (en) Hydrolysis-stable polyurethane for the coating of elements in marine applications
DE102004001317A1 (en) Polyurethane foams for pipe insulation
EP1595904A2 (en) Insulated pipe containg a polyurethane prepared with formic acid
EP3947501B1 (en) Insulated pipe, comprising an environmentally-friendly propellant blown polyurethane foam with low friability
EP2751157B1 (en) Method for producing insulated pipes having improved properties
EP2668237A2 (en) Polyurethane with improved insulating properties
EP0875528A1 (en) Process for the preparation of rigid polyurethane foams
EP2874808B1 (en) Method for continuous production of foams in pipes
EP2768650B1 (en) Method for improving physical properties in the manufacture of pipes preinsulated with plastic
EP3578582A1 (en) Rigid polyurethane foams with improved drying
WO2008025660A1 (en) Connections of coated media conduits

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA HR MK YU

17P Request for examination filed

Effective date: 20071025

AKX Designation fees paid

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: BASF SE

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 502006001116

Country of ref document: DE

Date of ref document: 20080828

Kind code of ref document: P

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: PL

Ref legal event code: T3

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080716

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080716

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081116

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081016

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081216

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080716

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081027

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080716

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

BERE Be: lapsed

Owner name: BASF SE

Effective date: 20081031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080716

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080716

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080716

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080716

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080716

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20081031

26N No opposition filed

Effective date: 20090417

REG Reference to a national code

Ref country code: HU

Ref legal event code: AG4A

Ref document number: E004998

Country of ref document: HU

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20081031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20081004

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080716

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080716

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081017

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20101004

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20101031

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20101031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20101004

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 10

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 11

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 12

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20231023

Year of fee payment: 18

Ref country code: IT

Payment date: 20231024

Year of fee payment: 18

Ref country code: HU

Payment date: 20230914

Year of fee payment: 18

Ref country code: FR

Payment date: 20231026

Year of fee payment: 18

Ref country code: FI

Payment date: 20231026

Year of fee payment: 18

Ref country code: DK

Payment date: 20231023

Year of fee payment: 18

Ref country code: DE

Payment date: 20231027

Year of fee payment: 18

Ref country code: AT

Payment date: 20231018

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: PL

Payment date: 20240910

Year of fee payment: 19